Non-precipitating alkali/alkaline earth metal and aluminum solutions made with diols having at least two primary hydroxyl groups

ABSTRACT

A stable catalyst solution suitable for catalyzing the polycondensation of reactants to make polyester polymers comprising:
         (i) M, wherein M is represented by an alkaline earth metal or alkali metal and   (ii) aluminum metal and   (iii) a polyhydroxyl solvent having at least 3 carbon atoms and at least two primary hydroxyl groups, the longest carbon chain being a hydrocarbon; such as 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, or combinations thereof,
 
wherein the molar ratio of M:Al ranges from 0.75:1 to less than 1.5:1. The catalyst solution is desirably a solution which does not precipitate upon standing over a period of at least one week at room temperature (25° C.-40° C.), even at molar ratios of M:Al approaching 1:1. There is also provided a method for the manufacture of the solution, its feed to and use in the manufacture of a polyester polymer, and polyester polymers obtained by combining certain ingredients or containing the residues of these ingredients in the composition.

This application claims priority to Provisional Application No.60/873,785 filed Dec. 8, 2006, fully incorporated herein by reference.

1. FIELD OF THE INVENTION

The invention pertains to aluminum based solutions useful in themanufacture of polyester polymers, and more specifically to catalystscomprising aluminum and alkaline earth metal or alkali metals which haveimproved solubility at low alkaline earth metal or alkali metal:aluminummolar ratios.

2. BACKGROUND OF THE INVENTION

Catalyst solutions prepared from alkaline earth metal or alkali metals(“M”) and aluminum tend to precipitate over time in ethylene glycol.This problem is especially noticeable as the molar ratio of M:Al inethylene glycol drops from 5:1 and approaches 1:1, where precipitationbegins to occur at moderate temperatures less than 125° C. It isdesirable that the feed of catalyst components to a melt phasepolymerization process stay in solution as fed to provide more uniformmixing with the reactants or polymer melt, and to enable feeding aconsistent and uniform amount of desired catalyst to the melt phaseprocess.

A catalyst solution has advantages over catalyst slurries, in that asolution avoids the potential for pumping and circulation problems,avoids transfer line fouling and plugging, and avoids the need forvigorous agitation used in slurries to prevent insoluble catalystprecipitates from settling in feed tanks. Precipitates in the feed tanksmake feeding a uniform feed of catalyst to the melt phase polymerizationprocess a problem. The amount of actual catalyst fed to a melt phasepolymerization line for making the polyester through a feed system setat a given flow rate will fluctuate if precipitates form, therebyleading to inconsistent product types or product quality.

Lithium hydroxide and aluminum isopropoxide can be combined in thepresence of ethylene glycol to form a solution. This can be accomplishedby heating the components to a temperature sufficient to form thecatalyst in solution. The temperature for this reaction is normally inthe range of 125° C. to 160° C. for one to five hours. Generally, theconcentration of aluminum in the solution cannot exceed 3,000 ppm due tolack of solubility.

Precipitates can form under several conditions when a catalyst system ismixed in ethylene glycol. Precipitates can form when the catalystsolution cools down to ambient temperatures. To maintain the catalystsin solution, an ethylene glycol/Li/Al catalyst composition must remainat an elevated temperature of about 150° C. or more, especially when themolar ratio is about 3:1 or less and approaches 1:1. To maintain thecatalyst solution at elevated temperatures requires increased plantcapital for heated catalyst feed vessels.

Another way precipitates form is when the amount of aluminum in thecatalyst composition exceeds 3000 ppm. It is desirable to employ acatalyst feed source having a high concentration of Al so that theamount of solvent fed to the melt phase process can be reduced. Dilutecatalyst systems can be used but suffer the drawback that a highervolume of the solution is fed to the melt phase process to meet a targetcatalyst metal content, thereby requiring the removal throughevaporation or reaction of larger amounts of solvent from the melt phaseprocess.

Not only can the catalyst precipitate in ethylene glycol solutions when3000 ppm aluminum or more is used or if the hot solution is allowed tocool, but it can precipitate as the molar ratio of M:Al approaches 1:1.However, we have discovered that a molar ratio of M:Al of about 1:1 isdesirable in some applications because the yellowness of the polyesterpolymer is minimized as the molar ratio of M:Al approaches 1:1.

Thus, it would be desirable to provide a catalyst composition whichremains in solution at ambient conditions without agitation.Alternatively, or in addition, it would also be desirable if solutionscan be made, if desired, at molar ratios of M:Al that approach 1:1 andare stable over a wide variety of temperatures, including ambientconditions. Alternatively, or in addition, it would be particularlyadvantageous if such solutions can be made using 3000 ppm Al or more tominimize the amount of solvent fed to a melt phase polycondensationprocess.

3. SUMMARY OF THE INVENTION

We have found that with the use of certain polyhydroxyl compounds,catalyst solutions can be prepared with improved solubility, which donot precipitate at ambient conditions over a period of at least one (1)week at low mole ratios of M:Al. Now there is provided a solutioncomprising:

-   -   (i) M, wherein M is represented by an alkaline earth metal or        alkali metal and    -   (ii) aluminum metal and    -   (iii) a polyhydroxyl solvent having at least 3 carbon atoms and        at least two primary hydroxyl groups, the longest carbon chain        being a hydrocarbon;        wherein the molar ratio of M:Al ranges from 0.75:1 to less than        1.5:1

There is also provided a polyester polymer solution comprising theresidue of this catalyst system and a polyester polymer, said catalystsystem obtained by combining

-   -   (i) M, wherein M is represented by an alkaline earth metal or        alkali metal and    -   (ii) aluminum metal and    -   (iii) a polyhydroxyl solvent having at least 3 carbon atoms and        at least two primary hydroxyl groups, the longest carbon chain        being a hydrocarbon;        wherein the molar ratio of M:Al ranges from 0.75:1 to less than        1.5:1

The solutions are useful to catalyze (increase the reaction rate) theformation of polyester polymers.

There is also provided another embodiment of a catalyst solution inwhich the amount of aluminum in the catalyst solution is greater than3000 ppm which remains in solution over a period of at least one (1)week.

There is also provided a method for the manufacture of the solution, itsfeed to and use in the manufacture of a polyester polymer, and polyesterpolymers obtained with these catalyst solutions.

4. DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to thefollowing detailed description of the invention.

It must also be noted that, as used in the specification and theappended claims, the singular forms “a,” “an” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to processing or making a “polymer,” a “preform,” “article,”“container,” or “bottle” is intended to include the processing or makingof a plurality of polymers, preforms, articles, containers or bottles.

References to a composition or solution containing “an” ingredient or“a” polymer is intended to include other ingredients or other polymers,respectively, in addition to the one named.

By “comprising” or “containing” or “having” is meant that at least thenamed compound, element, particle, or method step etc. must be presentin the composition, solution or article or method, but does not excludethe presence of other compounds, catalysts, materials, particles, methodsteps, etc., even if the other such compounds, material, particles,method steps etc. have the same function as what is named, unlessexpressly excluded in the claims.

It is also to be understood that the mention of one or more method stepsdoes not preclude the presence of additional method steps before orafter the combined recited steps or intervening method steps betweenthose steps expressly identified. Moreover, the lettering of processsteps is a convenient means for identifying discrete activities orsteps, and unless otherwise specified, recited process steps can bearranged in any sequence.

Expressing a range includes all integers and fractions thereof withinthe range. Expressing a temperature or a temperature range in a process,or of a reaction mixture, or of a melt or applied to a melt, or of apolymer or applied to a polymer means in all cases that the limitationis satisfied if either the applied temperature, the actual temperatureof the melt or polymer, or both are at the specified temperature orwithin the specified range.

The word “composition” or “solution” means that each listed ingredientis present in the composition or solution, and does not imply that anyingredient in the composition or solution is unbound or unreacted. Thecomposition may be solid or liquid. The stated ingredients in thecomposition may be bound, unbound, reacted, unreacted, and unlessotherwise specified, in any oxidation state. For example, specifying thepresence of “aluminum” or “Al” or “lithium” or “Li” means the atoms ofaluminum or lithium, respectively, and does not imply that they occupyany oxidation state, any morphological state, any structural state, orany chemical state, whether as added to or as present in the solution,polymer or composition of matter, unless such states are expresslystated.

As used herein, the term “metal” is a metal atom and does not imply anyoxidation state or its chemical state. Aluminum metal or an alkalineearth metal or alkali metal may be in any chemical state as a salt orchelate or complex or elemental, and in any oxidation state, unlessotherwise expressly stated as having a particular oxidation state. Theword “elemental,” however, means a zero oxidation state.

The reported amount of a metal (e.g. ppm) is based on the amount of themetal atom present in the solution, polymer, or article and not theamount of the compound or salt, unless expressly stated as the amount ofthe compound or salt.

The intrinsic viscosity (It.V.) values are set forth in dL/g unit andcalculated according to ASTM D 4603, whereby the inherent viscosity(Ih.V.) is measured at 30° C. in 60% phenol and 40%1,1,2,2-tetrachloroethane by weight at a concentration of 0.5 g/dL.

The weight of alkaline earth metal or alkali can be measured orcalculated upon addition to the melt phase or by analytical techniquesfor detecting the amount in the finished polymer or article. Suitabledetection methods for the presence of alkali metals or alkaline earthmetals include inductively coupled plasma optical emission spectroscopy(ICP-OES). The concentration of an alkaline earth metal or an alkalimetal or aluminum or phosphorus or any other element or metal isreported as the parts per million of metal atoms based on the weight ofthe polymer.

There is now provided a solution comprising:

-   -   (i) M, wherein M is represented by an alkaline earth metal or        alkali metal and    -   (ii) aluminum metal and    -   (iii) a polyhydroxyl solvent having at least 3 carbon atoms and        at least two primary hydroxyl groups, the longest carbon chain        being a hydrocarbon;        wherein the molar ratio of M:Al ranges from 0.75:1 to less than        1.5:1

The solution contains aluminum. The polyester polymers made with thesolutions also contain aluminum. The presence of aluminum in thepolyester polymer may be detected through any suitable analyticaltechnique regardless of the oxidation state of the aluminum. Suitabledetection methods for the presence of aluminum include inductivelycoupled plasma optical emission spectroscopy (ICP-OES). Theconcentration of aluminum is reported as the parts per million of metalatoms based on the weight of the polymer.

Reporting the concentration of aluminum or alkaline earth metal oralkali metals means the concentration of these atoms in the polymer, notthe concentration of the metal compounds used to make the solution.

In the preparation of the solution, aluminum may be added as a compound(which includes a salt or a complex), or as an elemental metal providedthat it is ultimately active as a catalyst in the polycondensation phaseeither alone or in combination with the alkali metal or alkaline earthmetal atoms or compounds.

In one aspect of the invention, catalytic aluminum compounds with atleast one organic substituent, or two, or three, are used in thepreparation of the solution. Illustrative examples of aluminum compoundssuitable as catalysts include those of the formula:

Al[OR]_(a)[OR']_(b)[OR″]_(c)[R′″]_(d)

wherein R, R′, R″ are independently an alkyl group, aryl group, acylgroup or hydrogen, R′″ is an anionic group, and a, b, c, d areindependently 0 or positive integers, and a+b+c+d is not greater than 3,or preferably equal to 3.

Aluminum compounds having catalytic activity include those which arecapable of increasing the reaction rate of a polymerization reaction, inparticular a condensation reaction such a those used to make polyesterpolymers (which can be measured as a reduction in residence time toreach a target It.V., or an increase in It.V. over time such as anincrease of at least 0.1 dL/g over 1 hour). The particular aluminumcompounds chosen are preferably those which are effective to increasethe It.V. of the reaction melt by at least 0.2 dL/g within 1 hour.

The specific type of aluminum compounds employed are desirably thosethat are not readily soluble in ethylene glycol. The types of aluminumcompounds that are not readily soluble will, when mixed with ethyleneglycol at a concentration of 3000 ppm, precipitate at ambient conditionswithout agitation within 2 days. While other aluminum compounds that arereadily soluble in ethylene glycol can be employed and are within thescope of the invention, they are often expensive or not commerciallyavailable. Thus, the invention provides the flexibility of providingsolutions employing a wide selection of aluminum compounds, even thosewhich are difficult to dissolve or are insoluble in ethylene glycol atambient conditions. Suitable examples of aluminum compounds include thecarboxylic acid salts of aluminum such as aluminum acetate, aluminumbenzoate, aluminum lactate, aluminum laurate, aluminum stearate,aluminum alcoholates such as aluminum ethoxide, aluminum isopropoxide,aluminum phenoxide, aluminum sec-butoxide, aluminum tert-butoxide,aluminum tributoxide, and aluminum chelates in which the alkoxy group ofan aluminum alcoholate is partially or wholly substituted by a chelatingagents such as aluminum ethyl acetoacetate diisopropoxide,bis(2-butanolato)aluminum ethyl acetoacetate, aluminum acetylacetonateand aluminum tris(ethyl acetoacetate).

The effects of the invention are particularly noticeable among thedifficult to dissolve or insoluble aluminum compounds in ethyleneglycol. Examples of these compounds include the basic carboxylic acidsalts of aluminum such as aluminum acetate, aluminum benzoate, aluminumlaurate, aluminum stearate, and aluminum alcoholates such as aluminumethoxide, aluminum isopropoxide, aluminum sec-butoxide, aluminumtert-butoxide, and aluminum tributoxide. In one aspect, the aluminumcompound comprises aluminum acetate, and aluminum isoproxide, andespecially aluminum isopropoxide.

An amount of aluminum atoms, in combination with M, are employed toeffect polycondensation once added to the melt phase polymerizationprocess. Suitable amounts of aluminum atoms present in the polymergenerally range from at least 3 ppm, or at least 5 ppm, or at least 10ppm, or at least 15 ppm, or at least 20 ppm, or at least 30 ppm, and upto about 150 ppm, or up to about 100 ppm, or up to about 75 ppm, or upto about 60 ppm, or up to 30 ppm, or up to 20 ppm, or up to 15 ppmaluminum atoms based on the weight of the polymer. The preferred rangeof aluminum loading in the polyester polymer is, and the amount ofaluminum atoms present in the solution fed to a melt phasepolymerization reactor is effective to provide in the polymer, 5 ppm to60 ppm, with the most preferred amount on a calculated basis rangingfrom 10 to 20 ppm Al based on the weight of the polymer.

Of course, the solution may and usually will contain a much higherconcentration of the metals than present in the polyester polymer. Thesolution is fed or metered to the melt phase at a rate corresponding tothe desired amount of metal present in the polyester polymer. Thesolution may contain any desired amount of aluminum, but generally from1000 ppm, or at least 2000 ppm, or greater than 3000 ppm, or at least3500 ppm, or at least 4000 ppm, or at least 5000 ppm, or at least 1 wt.% of Al or even up to 3 wt %. The maximum amount of aluminum used is upto its solubility limit in a given solvent mix at ambient conditions.High concentrations of aluminum are desirable so that the amount ofsolvent fed to the melt phase process is reduced and/or higher loadingsof aluminum can be fed to the melt phase process for making thepolyester polymer at a given flow rate in order to increase thepolycondensation reaction rate and thereby lower the polymerization timeand increase throughput.

In one embodiment, there is provided a catalyst solution containing atleast 3000 ppm aluminum, or at least 3500 ppm aluminum, or at least 4000ppm aluminum, or at least 10,000 ppm, and may contain up to 10 wt. % orup to 5 wt. % or up to 3 wt. % or up to 2 wt. % aluminum.

The alkali may be added as a metal compound or an organometalliccompound. The alkali metals and alkaline earth metals include the metalsin Group IA and Group IIA of the periodic table, including but notlimited to Li, Na, K, Rb, Cs, Mg, Ca, Sr, and preferably Li, Na or K. Ifrapid rates are the primary concern, Li or Na are generally preferred.The metals may be added to the melt phase as metal compounds (whichincludes a complex or a salt) having counterions, among which thepreferred ones are hydroxides, carbonates, and carboxylic acids.

The amount of alkaline earth metal or alkali, in combination with Al, iseffective to increase the molecular weight of the polymer melt. Theamount by weight will vary widely depending upon the molecular weight ofthe metal. The amount of the alkaline earth metal or alkali metal in thesolution may vary between at least 100 ppm, or at least 150 ppm, or atleast 250 ppm, or at least 500 ppm, or at least 700 ppm, or at least 780ppm, or at least 1000 ppm, or at least 2000 ppm, or at least 2460 ppm,or at least 3000 ppm, or at least 5000 ppm, or at least 1 wt. %, or atleast 2 wt. %, and up to about 30 wt. %, or up to about 20 wt. %, or upto 15 wt. %, or up to 10 wt. %, or up to 5 wt. %, or up to 2 wt. %, orup to 1 wt. %, or up to 5000 ppm, based on the weight of the solution.

The amount of alkaline earth metal or alkali metal fed to the melt phasepolymerization process is effective to produce a polyester polymercomposition containing, and the polyester polymer composition contains,from at least 1 ppm, or at least 2 ppm, or at least 3 ppm, or at least 4ppm, or at least 5 ppm, and up to about 60 ppm, or up to about 50 ppm,or up to about 30 ppm, or up to about 20 ppm, or up to about 15 ppm,alkaline earth metal or alkali metal on a calculated basis and based onthe weight of the polyester polymer composition.

The molar ratio of the alkaline earth metal or alkali:aluminum (M:Al) isdesirably at least 0.75:1, or at least 0.5:1, or at least 0.8:1, or atleast 0.85:1, or at least 0.9:1, or a least 0.95:1, and up to less than1.5:1, or up to 1.4:1, or up to 1.3:1, or up to 1.25:1, or up to 1.2:1,or up to 1.15:1, or up to 1.1:1, or up to 1.05:1. More examples ofsuitable ranges include 0.75:1 to 1.25:1, or 0.8:1 to 1.25:1, or 0.9:1to 1.1:1, or about 1:1.

It is desirable to provide a large number of Al atoms to increase thecatalytic activity of the catalyst system. Although not wishing to bebound to a theory, it is believed that aluminum is difficult to dissolvein ethylene glycol. Ethylene glycol has been a common carrier for a widevariety of solutions and/or dispersions since it is generally a reactantin the polymerization process for making a polyester polymer or ishighly compatible with the melt. It is now possible, however, using thesolvents described in the invention, to provide a solution which has alower tendency to precipitate even at higher levels of aluminum and/orat low temperatures and/or at molar ratios of M:Al approaching 1:1.

Stable solutions having molar ratios of M:Al approaching 1:1 areobtainable using the solvent described below, whereas stable solutionsemploying molar ratios of M:Al approaching 1:1 in ethylene glycol as thesole solvent are not obtainable. In this embodiment, a stable solutionthat does not precipitate over a period of at least one (1) week atambient conditions is obtainable at molar ratios of M:Al within a rangeof 0.75:1 to 1.5:1, or 0.9:1 to 1.25:1, or 0.9:1 to 1.1:1. We have foundthat solutions of ethylene glycol tend to be more stable as the molarratio of M:Al increases to 3:1 and beyond, but at molar ratiosapproaching 1:1, precipitates readily form upon cooling the solution toambient conditions. By contrast, the addition of the polyhydroxylsolvents described herein improves the solubility and stability ofcatalysts having a low molar ratio.

Not only are solutions prepared with polyhydroxyl solvents stable atambient conditions over a period of one (1) week at molar ratios of M:Alapproaching 1:1, (and by contrast ethylene glycol solutions are notstable at these low mole ratios at ambient conditions), but thesepolyhydroxyl solvents appear to be lose their effectiveness as the molarratio increases to 2:1 and beyond, while by contrast, ethylene glycolappears to be more effective at the higher molar ratios especially 5:1.

The polyhydroxyl solvent employed in the invention keeps the alkalineearth metal or alkali metal and aluminum metal combinations in solutionover a period of at least one (1) week at ambient conditions. Ambientconditions means a temperature between 25° C. and 40° C. and a pressureof about 1 atmosphere without agitation). A composition is deemed a“solution” when, if measured, no precipitates are visible by visualinspection to the naked eye after allowing the composition to standstill over a period of at least one (1) week at ambient conditions Inanother embodiment, the solubility of (i) and (ii) in the solvent at thegiven concentrations in a particular composition is sufficiently highsuch that, if measured, no precipitation is visible to the naked eyewhen the solution is allowed to stand still over a period of period ofat least two (2) weeks, or at least three (3) weeks, or at least four(4) weeks.

The solvent compound employed to maintain the catalyst system insolution is a polyhydroxyl solvent. The polyhydroxyl solvent has atleast two (2) primary hydroxyl groups. The polyhydroxyl solvent has atleast three (3) carbon atoms including the carbons bonded to thehydroxyl groups. The longest carbon chain of the polyhydroxyl compoundis a hydrocarbon, e.g, repeating consecutive carbons throughout thelongest carbon chain with each carbon having at least 1 hydrogen atom.As such, the hydrocarbon chain does not contain ether or ester or amidelinkages. However, the longest carbon chain in the polyhydroxyl solventmay be branched or unbranched, saturated or unsaturated, substituted orunsubstituted internal to the primary hydroxyl group carbon atoms

The solvent compound desirably has no more than two (2) hydroxyl groups.

The solvent compound is desirably unbranched.

The solvent compound is desirably linear.

The solvent compound desirably has no more than 8 carbon atoms, or nomore than 6 carbon atoms, or no more than 5 carbon atoms.

The solvent compound is desirably saturated, e.g. no unsaturation.

The two primary hydroxyl groups on the solvent compound are desirablyend groups.

The solvent compound desirably has no functional group other than the atleast two primary hydroxyl groups, and more preferably only two primaryhydroxyl groups.

The amount of polyhydroxyl solvent is sufficient to keep the aluminumand alkaline earth metal or alkali metals in solution. The polyhydroxylsolvent may be the sole solvent or may be combined with other diluents,solvents, or liquid carriers so long as the catalyst stays in solutionfor a period of at least one (1) week. The amount of polyhydroxylsolvent present in the solution, based on the weight of the solution, ispreferably sufficient to obtain a stable solution (no precipitation)after one week at ambient conditions (between 25° C.-40° C. and about 1atmosphere). The amount of polyhydroxyl solvent can vary widelydepending on the nature of other solvents used. Suitable amountsgenerally range from at least 30 wt. %, or from 35 wt. %, or from 40 wt.%, or from 45 wt. %, or from 50 wt. %, or from 60 wt. %, or from 70 wt.%, or from 75 wt. %, or from 80 wt. %, or from 90 wt. %, or from 95 wt.%, and up to 100%, based on the weight of all liquids in the solution.When mixed with ethylene glycol, the amount of polyhydroxyl solvent isdesirably at least 70 wt. %, or at least 75 wt. %, or at least 80 wt. %,or at least 90 wt. %, based on the weight of the solution

Examples of the polyhydroxyl solvent include and are not limited to1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, or combinationsthereof.

The solution is prepared by combining the alkaline earth metal or alkalisalts with the aluminum compounds, preferably a trivalent aluminumcompound, adding the polyhydroxyl solvent, and stirring the mixture at atemperature ranging from 20° C. to 150° C., or at 80° C. to 140° C.

In one embodiment, there is now also provided a process for making thesolution comprising subjecting a composition containing M, Al, and thepolyhydroxyl solvent to an inert gas sweep while heating, preferably toa temperature of at least 80° C. Such an inert gas sweep is desirable toavoid unwanted side reactions which may have the potential fordiscoloring the solution or inhibiting the solubility of thepolyhydroxyl solvent. An example of a suitable inert gas sweep is a gascomposition having a richer content of an inert gas than that found inthe atmosphere, such as having a nitrogen concentration richer than thatfound in the atmosphere, typically containing at least 90% nitrogen. Thevolumetric flow rate is not particularly limited and can be easilyadjusted to maintain the coloration of the solution within desiredlimits. Typical flow rates are at least 0.5 standard cubic feet per hour(SCFH), or at least 0.75 SCFH, or at least 1 SCFH, or at least 2 SCFH.Without being bound to a theory, it is believed that the inert gas sweepwill promote the escape from the solution of volatile by-products thatcontribute to the formation of color bodies or which inhibit solubility.The inert gas is swept across a surface of the solution for at least aportion of the heating cycle during which the solution is made to becomesoluble. In another aspect, the solution is subjected to a gas sweep atleast at the time when the solution obtains its highest temperatureduring preparation.

One or any combination of benefits and features are obtainable by thesolutions of the invention:

-   -   A. Stable solutions which do not precipitate at ambient        conditions over a period of at least one (1) week;    -   B. Solutions containing greater than 3000 ppm aluminum while        satisfying A above; and    -   C. Solutions which contain a molar ratio of M:Al approaching        1:1, such as ranging from 0.85:1 to 1.25:1, while satisfying A        above; and

There is also now provided a polyester polymer composition comprising acatalyst system and a polyester polymer, said catalyst system obtainedby combining

-   -   (i) M, wherein M is represented by an alkaline earth metal or        alkali metal and    -   (ii) aluminum metal and    -   (iii) a polyhydroxyl solvent having at least three (3) carbon        atoms and two (2) primary hydroxyl groups,        wherein the molar ratio of M:Al ranges from 0.75:1 to less than        1.5:1.

The aluminum metal is typically combined with (i) and (iii) in the formof a salt or compound, as is M, as noted above.

The polyester polymer produced in the melt phase may contain phosphorusatoms. Phosphorus may be added late in the melt phase polymerizationprocess to deactivate or stabilize the catalyst system, thereby reducingthe haze level of the polymer, bottle preforms, and bottles madethereby, even at high catalyst loadings. The polyester polymer maycontain phosphorus atoms in an amount ranging from 3 ppm to 500 ppm,based on the weight of the polymer composition. The amount of phosphorusis desirably at a mole ratio of P:M (all metals of aluminum and alkalineearth metals and alkali metals) within a range of 0.2:1 to 3:1. Typicalamounts of phosphorus atoms will be at least 3 ppm, or at least 5 ppm,or at least 10 ppm, or at least 50 ppm, or at least 100 ppm, and up to500 ppm, or up to 200 ppm, or up to 100 ppm, or up to 50 ppm, or up to30 ppm, or up to 15 ppm. The solution haze values of these polymers canbe as low as 30 ntu or less, or 20 ntu or less, or 15 ntu or less, or 10ntu or less. The relative reduction of haze by addition of phosphorus isas large as 40% or more, or 50% or more, or 60% or more, relative to thesame polymer made without phosphorus.

Other catalyst metals may be present if desired. For example, Mn, Zn,Sb, Co, Ti, and Ge catalysts may be used in conjunction with aluminumand alkaline earth metals or akali catalysts. Preferably, the polyesterpolymer is made without the addition of cobalt to the melt phasereaction since organic toners are preferred. Titanium catalysts can beused. The titanium catalysts are those compounds added in amounts whichincrease the It.V. of polyester melt by at least 0.3 dL/g if notdeactivated. The amount of titanium catalyst, if used, generally rangesfrom 2 ppm to 15 ppm, or up to 10 ppm, based on the weight of thepolymer. Antimony catalysts can also be used in combination with thecatalyst system of the invention. The amount of antimony can range from20 ppm to 250 ppm. Due to acetaldehyde (AA) generation concerns, theamount of antimony is preferred to be no greater than 125 ppm, based onthe weight of the polymer, and preferably there is provided a polyesterpolymer which does not contain any antimony added to its manufacture inthe melt phase.

In one embodiment, the polyester polymer contains aluminum, alkalineearth metal or alkali metals, and does not contain any antimony catalystin catalytic quantities, or does not contain any cobalt catalyst incatalytic quantities, or does not contain any titanium catalyst incatalytic quantities, or does not contain any germanium catalyst incatalytic quantities, or does not contain any combination of Ti, Co, Sb,or Ge based catalysts in catalytic quantities, or does not contain anyof the aforementioned catalyst metals (other than Al and alkaline earthmetal or alkali metals) added to the polymer during its manufacture inthe melt phase, or does not contain any catalyst metals other thanaluminum and an alkaline earth metal or alkali. A catalyst metal is saidto have catalytic activity if it increases the reaction rate orincreases the It.V. of the melt by at least 0.1 dL/g from a startingpoint of 0.2 to 0.4 dL/g after 1 hour at 280° C. and 0.8 mm Hg. It is tobe recognized, however, that one or more of metals such as cobalt ormanganese will most likely be present at low levels in the melt becausethey come as impurities with the terephthalic acid composition made froma metal-catalyzed, liquid-phase oxidation process. Metal impuritiespresent in the raw material supply to the melt phase process are notconsidered to be metals added to the melt phase process and they are notpresent in any event in catalytically effective quantities.

The “polyester polymer” is any thermoplastic polyester polymer.Polyester thermoplastic polymers of the invention are distinguishablefrom liquid crystal polymers and thermosetting polymers in thatthermoplastic polymers have no appreciable ordered structure while inthe liquid (melt) phase, they can be remelted and reshaped into a moldedarticle, and liquid crystal polymers and thermosetting polymers areunsuitable for the intended applications such as packaging or stretchingin a mold to make a container.

The polyester polymer is desirably a random polymer such that themonomer units in the polymer chain are randomly arranged rather thanarranged in a block fashion. The polyester polymer contains repeatingalkylene arylate units, such as alkylene terephthalate or alkylenenaphthalate repeat units in the polymer chain. More specific examples ofthese repeating units include ethylene terephthalate, ethylenenaphthalate, and trimethylene terephthalate.

More specific examples of polyester polymers comprise:

-   -   (i) a carboxylic acid component comprising at least 80 mole % of        the residues of terephthalic acid, derivates of terephthalic        acid, naphthalene-2,6-dicarboxylic acid, derivatives of        naphthalene-2,6-dicarboxylic acid, or mixtures thereof, and    -   (ii) a hydroxyl component comprising at least 40 mole %, or at        least 60 mole %, or at least 80 mole % of the residues of        ethylene glycol or 1,3-propane diol,        based on 100 mole percent of carboxylic acid component residues        and 100 mole percent of hydroxyl component residues in the        polyester polymer.

Typically, polyesters such as polyethylene terephthalate are made byreacting a diol such as ethylene glycol with a dicarboxylic acid as thefree acid or its C₁-C₄ dialkyl ester to produce an ester monomer and/oroligomers, which are then polycondensed to produce the polyester. Morethan one compound containing carboxylic acid group(s) or derivative(s)thereof can be reacted during the process. All the compounds that enterthe process containing carboxylic acid group(s) or derivative(s) thereofthat become part of said polyester product comprise the “carboxylic acidcomponent.” The mole % of all the compounds containing carboxylic acidgroup(s) or derivative(s) thereof that are in the product add up to 100.The “residues” of compound(s) containing carboxylic acid group(s) orderivative(s) thereof that are in the said polyester product refers tothe portion of said compound(s) which remains in the said polyesterproduct after said compound(s) is condensed with a compound(s)containing hydroxyl group(s) and further polycondensed to form polyesterpolymer chains of varying length.

More than one compound containing hydroxyl group(s) or derivativesthereof can become part of the polyester polymer product(s). All thecompounds that enter the process containing hydroxyl group(s) orderivatives thereof that become part of said polyester product(s)comprise the hydroxyl component. The mole % of all the compoundscontaining hydroxyl group(s) or derivatives thereof that become part ofsaid polyester product(s) add up to 100. The “residues” of hydroxylfunctional compound(s) or derivatives thereof that become part of saidpolyester product refers to the portion of said compound(s) whichremains in said polyester product after said compound(s) is condensedwith a compound(s) containing carboxylic acid group(s) or derivative(s)thereof and further polycondensed to form polyester polymer chains ofvarying length.

The mole % of the hydroxyl residues and carboxylic acid residues in theproduct(s) can be determined by proton NMR.

In another embodiment, the polyester polymer comprises:

-   -   (a) a carboxylic acid component comprising at least 90 mole %,        or at least 92 mole %, or at least 96 mole % of the residues of        terephthalic acid, derivates of terephthalic acid,        naphthalene-2,6-dicarboxylic acid, derivatives of        naphthalene-2,6-dicarboxylic acid, or mixtures thereof, more        preferably terephthalic acid or derivates of terephthalic acid,        and    -   (b) a hydroxyl component comprising at least 90 mole %, or at        least 92 mole %, or at least 96 mole % of the residues of        ethylene glycol or propane diol, more preferably ethylene        glycol,        based on 100 mole percent of the carboxylic acid component        residues and 100 mole percent of the hydroxyl component residues        in the polyester polymer.

The reaction of the carboxylic acid component with the hydroxylcomponent during the preparation of the polyester polymer is notrestricted to the stated mole percentages since one may utilize a largeexcess of the hydroxyl component if desired, e.g. on the order of up to200 mole % relative to the 100 mole % of carboxylic acid component used.The polyester polymer made by the reaction will, however, contain thestated amounts of aromatic dicarboxylic acid residues and ethyleneglycol residues.

Derivates of terephthalic acid and naphthalane dicarboxylic acid includeC₁-C₄ dialkylterephthalates and C₁-C₄ dialkylnaphthalates, such asdimethylterephthalate and dimethylnaphthalate.

Modifiers can be present in amount of up to 40 mole %, or up to 20 mole%, or up to 10 mole %, or up to 8 mole %, or up to 4 mole %, based onthe total moles of their respective component in the polymer. Mono, triand higher functional modifiers are preferably present in amounts ofonly up to about 8 mole %, or up to 4 mole %.

In addition to a diacid component of terephthalic acid, derivates ofterephthalic acid, naphthalene-2,6-dicarboxylic acid, derivatives ofnaphthalene-2,6-dicarboxylic acid, or mixtures thereof, the carboxylicacid component(s) of the present polyester may include one or moreadditional modifier carboxylic acid compounds. Such additional modifiercarboxylic acid compounds include mono-carboxylic acid compounds,dicarboxylic acid compounds, and compounds with a higher number ofcarboxylic acid groups. Examples include aromatic dicarboxylic acidspreferably having 8 to 14 carbon atoms, aliphatic dicarboxylic acidspreferably having 4 to 12 carbon atoms, or cycloaliphatic dicarboxylicacids preferably having 8 to 12 carbon atoms. More specific examples ofmodifier dicarboxylic acids useful as an acid component(s) are phthalicacid, isophthalic acid, naphthalene-2,6-dicarboxylic acid,cyclohexane-1,4-dicarboxylic acid, cyclohexanediacetic acid,diphenyl-4,4′-dicarboxylic acid, succinic acid, glutaric acid, adipicacid, azelaic acid, sebacic acid, and the like, with isophthalic acid,naphthalene-2,6-dicarboxylic acid, and cyclohexane-1,4-dicarboxylic acidbeing most preferable. It should be understood that use of thecorresponding acid anhydrides, esters, and acid chlorides of these acidsis included in the term “carboxylic acid”. It is also possible fortricarboxyl compound branching agents and compounds with a higher numberof carboxylic acid groups to modify the polyester, along withmonocarboxylic acid chain terminators.

In addition to a hydroxyl component comprising ethylene glycol, thehydroxyl component of the present polyester may include additionalmodifier polyhydroxyls, diols, or compounds with a higher number ofhydroxyl groups. Examples of modifier hydroxyl compounds includecycloaliphatic diols preferably having 6 to 20 carbon atoms and/oraliphatic diols preferably having 3 to 20 carbon atoms. More specificexamples of such diols include diethylene glycol; triethylene glycol;1,4-cyclohexanedimethanol; propane-1,3-diol; butane-1,4-diol;pentane-1,5-diol; hexane-1,6-diol; 3-methylpentanediol-(2,4);2-methylpentanediol-(1,4); 2,2,4-trimethylpentane-diol-(1,3);2,5-ethylhexanediol-(1,3); 2,2-diethyl propane-diol-(1,3);hexanediol-(1,3); 1,4-di-(hydroxyethoxy)-benzene;2,2-bis-(4-hydroxycyclohexyl)-propane;2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane;2,2-bis-(3-hydroxyethoxyphenyl)-propane; and2,2-bis-(4-hydroxypropoxyphenyl)-propane.

As modifiers, the polyester polymer may preferably contain suchcomonomers as isophthalic acid, naphthalane dicarboxylic acid,1,4-cyclohexanedimethanol, and diethylene glycol.

The polyester composition may include blends of polyalkyleneterephthalates and/or polyalkylene naphthalates along with otherthermoplastic polymers such as polycarbonate (PC) and polyamides. It ispreferred that the polyester composition should comprise a majority ofthe polyester polymers, more preferably in an amount of at least 80 wt.%, or at least 95 wt. %, and most preferably 100 wt. %, based on theweight of all thermoplastic polymers (excluding fillers, inorganiccompounds or particles, fibers, impact modifiers, or other polymerswhich may form a discontinuous phase). It is also preferred that thepolyester polymers do not contain any fillers, fibers, or impactmodifiers or other polymers which form a discontinuous phase.

In one embodiment, the composition contains less than 60 wt %, or lessthan 40 wt %, or less than 20 wt. %, or less than 10 wt. %, or less than5 wt. %, or no post consumer recycle polyester polymer (“PCR”) presentin the composition. In another embodiment, the composition contains PCRin an amount of greater than zero and up to 60 wt. %, or up to 40 wt. %,or up to 20 wt %, or up to 10 wt. %.

Specific examples of the phosphorus compounds mentioned above assuitable catalyst deactivators and/or stabilizers include phosphoricacid, pyrophosphoric acid, phosphorous acid, polyphosphoric acid,carboxyphosphonic acids, phosphonic acid derivatives, and each of theiracidic salts and acidic esters and derivatives, including acidicphosphate esters such as phosphate mono- and di-esters and non-acidicphosphate esters (e.g. phosphate tri-esters) such as trimethylphosphate, triethyl phosphate, tributyl phosphate, tributoxyethylphosphate, tris(2-ethylhexyl) phosphate, oligomeric phosphatetri-esters, trioctyl phosphate, triphenyl phosphate, tritolyl phosphate,(tris)ethylene glycol phosphate, triethyl phosphonoacetate, dimethylmethyl phosphonate, tetraisopropyl methylenediphosphonate, mono-, di-,and tri-esters of phosphoric acid with ethylene glycol, diethyleneglycol, or 2-ethylhexanol, or mixtures of each. Other examples includedistearylpentaerythritol diphosphite, mono- and di-hydrogen phosphatecompounds, phosphite compounds, certain inorganic phosphorus compoundsthat are preferably soluble in the polymer melt, poly(ethylene)hydrogenphosphate, silyl phosphates; phosphorus compounds used in combinationswith hydroxy- or amino-substituted carboxylic acids, such as methylsalicylate, maleic acid, glycine, or dibutyl tartrate; each useful forinactivating metal catalyst residues. Haze in solutions of particles orin molded parts is one indication of lack of solubility. Solubleadditives are more likely to deactivate/stabilize the catalyst system.

Other phosphorus compounds which may be added include the amine salts ofphosphorus-containing acids. The amines may be cyclic or acyclic, may bemonomeric, oligomeric, or polymeric, and should be selected so as tominimize haze and/or solubility when the latter are issues. The organicconstituents of the amine may in principle be any organic group. Ammoniaand related compounds like ammonium hydroxide are suitable.

To minimize It.V. loss if large quantities of phosphorus are added, orto further minimize the potential It.V. loss even if moderate or optimalquantities of phosphorus are added, it is desirable to add thephosphorus compound neat, that is without further dilution, such as inthe case of 85% or more phosphoric acid. If a carrier is used, it ispreferred that that the carrier is nonreactive, that is, does not breakthe polymer chain nor increase M generation rates. Water, alcohols,glycols and lower molecular weight PET are known to break the polymerchain. Once the minimum amount of the phosphorus compound and theassociated It.V. loss are known, the melt-phase process can be carriedout such that the It.V, made before deactivation/stabilization, ishigher by the amount of It.V. loss expected so that the target ItV. canbe achieved.

The melt phase reaction proceeds in a batch, semi-batch, or continuousmode. Preferably, the process of the invention is continuous.

The catalyst solution may be added after completion of esterification,or between the esterification zone and polycondensation zone, or at apoint when polycondensation starts, or during prepolymerization. In oneembodiment, the catalyst solution is added after 50%, or after 80%, orafter 90% conversion of the esterification reaction mixture. In anotherembodiment, the catalyst solution is added between the esterificationzone and inception of or during polycondensation or at the inception ofor during prepolymerization.

In another embodiment, the catalyst solution is added at any point toupon or after completion of esterification (at least 90% conversion) upto when the It.V. of the polyester melt reaches 0.3 dL/g, or no laterthan when the It.V. of the melt reaches 0.2 dL/g, and more preferably tothe oligomer mixture exiting the esterification zone or prior tocommencing or at the start of polycondensation.

If the molar ratio of the catalyst solution is not the molar ratio ofM:Al desired in the melt phase to polymerize the polyester melt, thepresent invention allows one the flexibility of feeding to the meltphase a stream of the stable catalyst solution of the invention whilealso feeding to the melt phase process a separate stream of alkalineearth metal or alkali M. In this way, one obtains the benefit ofemploying a stable catalyst solution having a molar ratio of M:Alranging from 0.5:1 to 1.5:1 to minimize yellow color body formation inthe polymer melt, while retaining the flexibility of increasing themolar ratio of M:Al as high as desired to increase the polycondensationrate and reduce residence time on either the same manufacturing linewhen a change to a different product is desired, or when one catalysttank is used to feed at least two lines, with the second line having aseparate feed of the alkaline earth metal or alkali metal. The advantageof this system allows one the flexibility to quickly change over to newproducts on the same line while utilizing the inventory in a catalystfeed tank from product to product, or to make a variety of polymershaving differing characteristics on different lines fed by the samecatalyst mix tank, with the first line fed by the catalyst solution, andthe second line (or other lines) fed by the same catalyst solution inaddition to the desired amount of additional alkaline earth metal oralkali metal feeds. More than one alkaline earth metal or alkali metalmay be fed to a melt phase line in addition to the catalyst solution,and the alkaline earth metal or alkali metal in the separate feed may bethe same or different from the alkaline earth metal or alkali metal usedin the catalyst solution.

The catalyst solution of the invention can be fed at any point in themelt phase process as described above, while simultaneously feeding aseparate stream of alkaline earth metal or alkali M earlier or later orat the same feed point as the catalyst solution feed point, preferablyearlier or at the same point, to adjust the desired M:Al molar ratio asneeded. For example, a stream of the alkaline earth metal or alkali Mcan be fed to the esterification zone and before 90% conversion, orbefore 70% conversion, or before 50% conversion, or before 40%conversion, or before 20% conversion, while the catalyst solution can befed at a point between 90% conversion in esterification and thepolycondensation zone when the It.V. of the melt is less than 0.3 dL/g.Both feeds can occur simultaneously in a continuous process for makingthe polyester polymer. The feed stream of alkaline earth metal or alkalimetals can be the same or different alkaline earth metals or alkalimetals employed in the catalyst solution. For example, M may be Li inthe catalyst solution containing Al, and M may be Na or K in the splitfeed stream. This allows even further flexibility in using two or moredifferent alkaline earth metal or alkali metal M in the same melt phasepolymerization line or process if desired

In one embodiment where the phosphorus compound is added to a melt phasepolymerization process, the catalyst stabilizer is added to thepolyester melt late during the course of polycondensation and beforesolidification. The deactivator is added to the polyester melt late inthe course of the polycondensation reaction when one or more of thefollowing conditions are satisfied or thereafter and beforesolidification of the polyester melt:

-   -   a) the polyester melt reaches an It.V. of at least 0.50 dL/g or    -   b) vacuum applied to the polyester melt, if any, is released, or    -   c) if the polyester melt is present in a melt phase        polymerization process, adding the phosphorus compound within a        final reactor for making the polyester polymer or between the        final reactor and before a cutter for cutting the polyester        melt, or    -   d) if the polyester melt is present in a melt phase        polymerization process, following at least 85% of the time for        polycondensing the polyester melt; or    -   e) the It.V. of the polyester melt is within +/−0.15 dl/g of the        It.V. obtained upon solidification; or    -   f) at a point within 20 minutes or less of solidifying the        polyester melt.

In one embodiment, the deactivator is added to the polyester melt afterthe polyester melt obtains an It.V. of at least 0.50 dL/g, or at least0.55 dL/g, or at least 0.60 dL/g, or at least 0.65 dL/g, or at least0.68 dL/g, or at least 0.70 dL/g, or at least 0.72 dL/g or at least 0.76dL/g, or at least 0.78 dL/g, and most preferably, regardless of when thedeactivator is added, the resulting polymer exiting the melt phasemanufacture has an It.V. of at least 0.68 dl/g.

In another embodiment, the deactivator is added to the polyester meltduring or after releasing the vacuum from the polyester melt undergoingpolycondensation reactions, or after bringing the pressure in apolycondensation zone or reactor to a level of 300 mm Hg or greater, or450 mm Hg or greater, or 600 mm Hg or greater, or to atmosphericpressure or greater, and preferably before the polyester melt issolidified.

In another embodiment, the deactivator is added at a location near or atthe end of a final reactor or between the final reactor and before acutter. For example, the deactivator is added to the lastpolycondensation reactor at a location proximal to the outlet of thelast polycondensation reactor, or to a pipe connecting directly orindirectly the last polycondensation reactor and a gear pump or extruderproviding the motive force to drive the melt through a die plate forcutting wherein said pipe is directed back to or proximal to the outletor the bottom of the last polycondensation reactor, or to a pipe inletto the last polycondensation reactor.

In yet another embodiment, the deactivator is added to the polyestermelt following at least 85%, or at least 90%, or at least 95%, or atleast 98%, or about 100% of the polycondensation time. Thepolycondensation time is measure as the time elapsed between the startof polycondensation zone to the exit of the polyester melt from the lastpolycondensation reactor.

In a further embodiment, the deactivator is added to the polyester meltwhen the It.V. of the polyester melt is within 0.10 dL/g, or within 0.05dl/g, or within 0.030 dL/g, or within 0.02 of the It.V. obtained uponsolidification.

In yet another embodiment, the deactivator is added to the polyestermelt at a point within 20 minutes, or within 10 minutes or less, or 5minutes or less, or 3 minutes or less of solidifying the polyester melt.The solidification of the polyester melt typically occurs when the meltis forced through a die plate into a water bath and cut into pellets, orin a melt-to-mold process when the melt is injection molded into amolded article.

In yet a more preferred embodiment, each of the embodiments identifiedherein occurs in a continuous manufacturing process where the throughputof the melt phase process on one manufacturing line is at least 1ton/day, or at least 50 tons/day, or at least 100 tons/day, or at least200 tons/day, or at least 300 tons/day, or at least 400 tons/day, or atleast 500 tons/day of polyester polymer in a steady state operation.

The reaction time of the melt from an It.V. of 0.40 dL/g through and upto an It.V. in the range of at least 0.68 dL/g to 0.94 dL/g is 150minutes or less, or 120 minutes or less, or 90 minutes or less, or 50minutes or less. The target It.V. is preferably between 0.84 and 0.94dL/g prior to deactivation/stabilization, the vacuum applied ispreferably between 0.5 and 1.0 torr, and temperature is preferablybetween 275° C. to 285° C.

Stabilizing or deactivating the catalyst late or near the end of a meltphase process can result in polyester particles that, in the absence ofacetaldehyde (AA) scavengers, generate less AA during subsequent meltprocessing. With late addition of a phosphorus compound, Al/alkalineearth metal or alkali catalyst systems can produce polyester polymerswith lower AA generation rates than polyester polymers made without thepresence of a catalyst deactivator or polyesters made with conventionalantimony catalysts that are similarly deactivated late with a phosphoruscompound. With late addition of a phosphorus compound to the polyestermelt catalyzed with an aluminum/alkaline earth metal or alkali system,it is now possible to obtain a polyester polymer having free AA levelsand an AA generation rate low enough for use in water bottleapplications without the need to add AA scavengers or other AA loweringadditives. Moreover, this type of polymer having both low free AA levelsand low AA generation rates without the presence of an AA loweringadditive can be obtained to a high It.V. (at least 0.68 dL/g, or atleast 0.70 dL/g, or at least 0.72 dL/g, or at least 0.74 dL/g, or atleast 0.76 dL/g, or at least 0.80 dL/g, or at least 0.84 It.V.) in themelt phase without the necessity for polymerizing the polymer in thesolid-state. Some catalyst combinations, some phosphorus levels in PETfrom late addition, and some water bottle specifications may necessitatea brief AA stripping treatment to lower free AA below 2 ppm prior tobeginning the injection molding process.

The polyester polymer made with the catalyst solution, and the polyesterpolymers used to make the preforms, bottles, and other articles, have anIt.V. which is preferably at least 0.68 dL/g, or at least 0.70 dL/g, orat least 0.72 dL/g, or at least 0.74 dL/g, or at least 0.76 dL/g, or atleast 0.80 dL/g, or at least 0.84 It.V., obtained in the melt phasepolymerization.

The polyester polymer compositions made with the composition, whenpartially crystallized to a degree of crystallinity of at least 20%, orat least 30%, or at least 35%, or at least 40%, have an L* of at least70, or at least 73, or at least 76, or at least 79, and an It.V. of atleast 0.70 dL/g, or at least 0.72 dL/g, or at least 0.76 dL/g obtainedfrom the melt phase.

The particles of the invention may be directly or indirectly packaged asa bulk into shipping containers, which are then shipped to customers ordistributors. It is preferred that the particles in the shippingcontainers are not solid state polymerized, and more preferably, theirIt.V. is not lower than the It.V. of the preforms or other articles madefrom the particles. It is desirable that the It.V. of the particles inthe shipping containers is the final It.V. desired to make the preformsuch that the It.V. of the particles is not subsequently increased inthe solid state. The shipping containers are desirably shipped to acustomer for making articles from the particles.

Shipping containers are containers used for shipping over land, sea orair. Examples include railcars, semi-tractor trailer containers, Gaylordboxes, ship hulls, or any other container which is used to transportfinished polyester particles to a customer. Customers are typicallyconverter entities who convert the particles into preforms or othermolded articles.

The shipping containers contain a bulk of polyester polymer particles. Abulk occupies a volume of at least 1 cubic meter, or at least 3 cubicmeters, or at least 5 cubic meters, or at least 10 cubic meters, or atleast 15 cubic meters. In preferred embodiments, the bulk in theshipping container occupies a volume of at least 5 cubic meters, or atleast 10 cubic meters.

In one embodiment, there is provided finished polyester polymerparticles having an average It.V. of at least 0.68 dL/g, or 0.70 dL/g,or 0.72 dL/g, or 0.74 dL/g, or 0.76 dL/g, obtained in a melt phasepolymerization and a residual acetaldehyde level of 10 ppm or less or of5 ppm or less; wherein said particles contain aluminum in an amount ofat least 3 ppm, or at least 5 ppm, or at least 10 ppm, or at least 15ppm, or at least 20 ppm based on the weight of the polymers, and furthercontain the residues of a polyhydroxyl solvent either reacted into thepolyester chain, reacted as an end group on the polyester chain, orreacted on a polyester polymer by transesterification. The solvent maybe reacted into the polyester chain during melt phase polymerizationsuch that the polyester polymer contains one unit or random repeat unitsof the polyhydroxyl solvent residue. Preferably, the polyester particlesin the shipping container also have a degree of crystallinity of atleast 20%, preferably at least 30%; and the particles also contain anonzero level of an alkaline earth metal or alkali metal, along with anonzero level of phosphorus. The particles are desirably contained in ashipping container. Most preferably, the particles have not been solidstate polymerized. By “finished” particles is meant particles that havebeen subjected by the particle manufacturer to all the processingconditions needed to produce a particle ready for feeding into dryerhoppers associated with a molding machine or directly to a moldingmachine used for converting particles into articles, without any furtherprocessing steps performed by the particle manufacturer.

Suitable articles which are formed from the polyester polymercompositions manufactured with the composition of the invention aresheets, bottle preforms, beverage bottle preforms, and blow moldedbottles made therefrom.

This invention can be further illustrated by the additional examples ofembodiments thereof, although it will be understood that these examplesare included merely for purposes of illustration and are not intended tolimit the scope of the invention.

EXAMPLES

The solutions of the invention may exhibit haziness yet constitutesolutions in which no precipitation occurs. Precipitates are deemedformed when by the eye one can observe the presence of the catalystmetal particulates settled at the bottom of the vessel.

Example 1

Preparation of a 1:1 Li:Al solution in 1,5-pentanediol: A 100 mL roundbottom flask was charged with 565 mg Al(O^(i)Pr)₃ (aluminumisopropoxide), 115 mg LiOH.H₂O, and 25 g 1,5-pentanediol and heated to130° C. with stirring and a nitrogen sweep for 4 hours. The solution wasclear at the end of the heating period and remained clear for greaterthan 35 days without agitation when held at ambient temperature andatmospheric conditions.

Example 2

Preparation of a 1:1 Li:Al solution in 1,4-butanediol: A 100 mL roundbottom flask was charged with 565 mg Al(O^(i)Pr)₃, 115 mg LiOH.H₂O, and25 g 1,4-buttanediol and heated to 130° C. with stirring and a nitrogensweep for 4 hours. The solution was clear at the end of the heatingperiod and remained clear for greater than 35 days when held withoutagitation at ambient temperature and atmospheric conditions.

Example 3

Preparation of a 1:1 Li:Al solution in 1,4-butanediol: A 100 mL roundbottom flask was charged with 2.83 g Al(O^(i)Pr)₃, 575 mg LiOH.H₂O, and30 g 1,4-butanediol and heated to 130° C. with stirring and a nitrogensweep for 4 hours. While the solution was never completely clear, ICPanalysis of a filtrate indicated that the solution contained 1.1 wt % Aland 0.277 wt % Li, thus giving some indication of the capacity of1,4-butanediol as a solvent. Although the solution never becamecompletely clear, the insoluble portion of the system consisted of veryfine particles consistent with hydrolyzed aluminum impurities. Noprecipitation was observed with this sample for greater than 20 days atambient temperature and atmospheric conditions without agitation.

Example 4

Preparation of a 1:1 Li:Al solution in 1,3-propanediol: A 100 mL roundbottom flask was charged with 565 mg Al(O^(i)Pr)₃, 115 mg LiOH.H₂O, and25 g 1,3-propanediol and heated to 130° C. with stirring and a nitrogensweep for 4 hours. The solution was clear at the end of the heatingperiod and remained clear for 11 days at ambient temperature andatmospheric conditions without agitation. After 11 days, precipitationbegan to occur.

Comparative Example 5

Preparation of a 1:1 Li:Al solution in 1,2-propanediol: A 100 mL roundbottom flask was charged with 565 mg Al(O^(i)Pr)₃, 115 mg LiOH.H₂O, and25 g 1,2-propanediol and heated to 130° C. with stirring and a nitrogensweep for 4 hours. The solution was clear at the end of the heatingperiod, but had precipitated substantially after less than 24 hours atambient temperature and atmospheric conditions without agitation. Thispolyhydroxyl compound, while having at least 3 carbon atoms, does nothave at least two primary hydroxyl groups.

Comparative Example 6

Preparation of a 1:1 Li:Al solution in ethylene glycol: A 200 mL roundbottom flask was charged with 2.27 g Al(O^(i)Pr)₃, 460 mg LiOH.H₂O, and100 g ethylene glycol and heated to 150° C. with stirring and a nitrogenpurge for 2 hours. A clear solution was obtained at the end of theheating period, but precipitation began to occur within 24 hours ofcooling to ambient temperature at atmospheric conditions withoutagitation. This polyhydroxyl compound does not contain at least 3 carbonatoms.

Comparative Example 7

Preparation of a 5:1 Li:Al solution in 1,5-pentanediol: A 100 mL roundbottom flask was charged with 565 mg Al(O^(i)Pr)₃, 575 mg LiOH.H₂O, and25 g 1,5-pentanediol and heated to 130° C. with stirring and a nitrogensweep for 4 hours. The reaction mixture never became completely clearand further precipitated overnight at ambient conditions and atmosphericconditions without agitation. While this polyhydroxyl compound had atleast 3 carbon atoms and two primary hydroxyl groups, the molar ratio ofLi:Al exceeded 1.5:1.

Comparative Example 8

Preparation of a 2:1 Li:Al solution in 1,4-butanediol: A 100 mL roundbottom flask was charged with 565 mg Al(O^(i)Pr)₃, 230 mg LiOH.H₂O, and25 g 1,4-butanediol and heated to 130° C. with stirring and a nitrogensweep for 4 hours. The reaction mixture never became completely clearwith significant solid particles remaining in the mixture. While thispolyhydroxyl compound had at least 3 carbon atoms and two primaryhydroxyl groups, the molar ratio of Li:Al exceeded 1.5:1

Comparative Example 9

Preparation of a 3:1 Li:Al solution in 1,4-butanediol: A 100 mL roundbottom flask was charged with 565 mg Al(O^(i)Pr)₃, 345 mg LiOH.H₂O, and25 g 1,4-butanediol and heated to 130° C. with stirring and a nitrogensweep for 4 hours. The reaction mixture never became completely clearwith significant solid particles remaining in the mixture. While thispolyhydroxyl compound had at least 3 carbon atoms and two primaryhydroxyl groups, the molar ratio of Li:Al exceeded 1.5:1.

Comparative Example 10

Preparation of a 1:1 Li:Al solution in 1,3-butanediol: A 200 mL roundbottom flask was charged with 1.13 g Al(O^(i)Pr)₃, 230 mg LiOH.H₂O, and50 g 1,3-butanediol and heated to 130° C. with stirring and a nitrogenpurge for 4 hours. A clear solution was obtained, however, upon closerexamination the reaction mixture appeared to have formed a gel and not asolution. This polyhydroxyl compound does not contain at least twoprimary hydroxyl groups.

1. A solution comprising: (i) M, wherein M is represented by an alkalineearth metal or alkali metal and (ii) aluminum metal and (iii) apolyhydroxyl solvent having at least 3 carbon atoms and at least twoprimary hydroxyl groups, the longest carbon chain being a hydrocarbon;wherein the molar ratio of M:Al ranges from 0.75:1 to less than 1.5:1.2. The solution of claim 1, wherein the solution is sufficiently stablesuch that, if measured, no precipitation is visible to the naked eyewhen the solution is allowed to stand still over a period of period ofat least one (1) week at ambient conditions.
 3. The solution of claim 2,wherein the solution is sufficiently stable such that, if measured, noprecipitation is visible to the naked eye when the solution is allowedto stand still over a period of at least three (3) weeks at ambientconditions.
 4. The solution of claim 1, wherein aluminum is obtainedfrom an aluminum compound represented by the formula:Al[OR]_(a)[OR′]_(b)[OR″]_(c)[R′″]_(d) wherein R, R′, R″ areindependently an alkyl group, aryl group, acyl group or hydrogen, R′″ isan anionic group, and a, b, c, d are independently 0 or positiveintegers, and a+b+c+d is not greater than
 3. 5. The solution of claim 4,wherein the aluminum compound comprises carboxylic acid salts ofaluminum.
 6. The solution of claim 5, wherein the aluminum compoundcomprises aluminum alcoholates.
 7. The solution of claim 2, wherein thealuminum is obtained from aluminum acetate or aluminum isoproxide orboth.
 8. The solution of claim 1, wherein the solution contains at least3000 ppm aluminum based on the weight of the solution.
 9. The solutionof claim 1, wherein the solution contains at least 5000 ppm aluminumbased on the weight of the solution.
 10. The solution of claim 1,wherein the solution contains at least 1 wt. % aluminum based on theweight of the solution.
 11. The solution of claim 1, wherein M compriseslithium, sodium, potassium, or combinations thereof.
 12. The solution ofclaim 11, wherein M comprises Li.
 13. The solution of claim 1, whereinthe molar ratio M:Al is at least 0.85:1.
 14. The solution of claim 1,wherein the molar ratio M:Al ranges from 0.75:1 to 1.3:1.
 15. Thesolution of claim 1, wherein the molar ratio M:Al ranges from 0.75:1 to1.25:1.
 16. The solution of claim 1, wherein the molar ratio M:Al rangesfrom 0.8:1 to 1.25:1
 17. The solution of claim 1, wherein the molarratio M:Al ranges from 0.85:1 to 1.2:1
 18. The solution of claim 1,wherein the molar ratio M:Al ranges from 0.9:1 to 1.15:1
 19. Thesolution of claim 1, wherein the molar ratio M:Al ranges from 0.75:1 to1.1:1
 20. The solution of claim 1, wherein the concentration of Al atomsis at least 3000 ppm, and the molar ratio of M:Al ranges from 0.8:1 to1.2:1.
 21. The solution of any one of claims 1-20, wherein the solventcomprises 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, orcombinations thereof.
 22. The solution of claim 1, wherein the primaryhydroxyl groups are the only end group reactive functionalities on thesolvent compound.
 23. The solution of claim 1, wherein the solutioncomprises said solvent in an amount of at least 60 wt. % based on theweight of liquids in the solution.
 24. The solution of claim 1, whereinthe solution comprises said solvent in an amount of at least 80 wt. %based on the weight of liquids in the solution.
 25. The solution ofclaim 1, wherein M comprises Li, the amount of Al in the solution is atleast 3000 ppm, the molar ratio of Li:Al ranges from 0.75:1 to 1.3:1,and solution is sufficiently stable such that, if measured, noprecipitation is visible to the naked eye when the solution is allowedto stand still over a period of period of at least one (1) week atambient conditions.
 26. The solution of claim 25, wherein the solventcomprises comprises 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol,or combinations thereof.
 27. The solution of claim any one of claims25-26, wherein said period is at least three (3) weeks and the molarratio of M:Al ranges from 0.8:1 to 1.2:1.
 28. A polyester polymercomposition comprising a catalyst system and a polyester polymer, atleast part of said catalyst system obtained by a solution comprising (i)M, wherein M is represented by an alkaline earth metal or alkali metaland (ii) aluminum metal and (iii) a polyhydroxyl solvent having at least3 carbon atoms and at least two primary hydroxyl groups, the longestcarbon chain being a hydrocarbon; wherein the molar ratio of M:Al rangesfrom 0.75:1 to less than 1.5:1.
 29. The polyester polymer composition ofclaim 28, wherein the polyester polymer comprises a polyethyleneterephthalate polymer.
 30. The polyester polymer composition of claim29, wherein M comprises lithium, sodium or potassium, and theconcentration of Al in the solution is at least 3000 ppm.
 31. Thepolyester polymer composition of claim 30, wherein M comprises lithium.32. The polyester polymer composition of claim 29, wherein thecomposition further comprises residues of phosphorus.
 33. The polyesterpolymer composition of claim 29, wherein M comprises Li, and the molarratio Li:Al ranges from 0.75:1 to 1.2:1.
 34. The polyester polymercomposition of claim 29, wherein the polyester polymer has an lt.V. ofat least 0.70 dL/g obtained from a melt phase polymerization process.35. The polyester polymer composition of claim 29, wherein said solventcomprises 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, orcombinations thereof.
 36. The polyester polymer composition of claim 28,wherein said polyester polymer has an lt.V. of at least 0.70 dL/gobtained from a melt phase polymerization process, M comprises Li, andthe molar ratio of Li:Al ranges from 0.75:1 to 1.2:1.
 37. The polyesterpolymer composition of claim 36, wherein the solvent comprises1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, or combinationsthereof.
 38. A bottle preform obtained from the polyester polymercomposition of claim
 28. 39. A beverage bottle obtained from thepolyester polymer composition of claim
 28. 40. A process for making apolyester polymer composition comprising adding a solution to a meltphase polymerization process for making a polyester polymer, saidsolution comprising: (i) M, wherein M is represented by an alkalineearth metal or alkali metal and (ii) aluminum metal and (iii) apolyhydroxyl solvent having at least 3 carbon atoms and at least twoprimary hydroxyl groups, the longest carbon chain being a hydrocarbon;wherein the molar ratio of M:Al ranges from 0.75:1 to less than 1.5:1.41. The process of claim 40, wherein after the addition of saidsolution, a phosphorus compound is added to the melt phasepolymerization process.
 42. The process of claim 40, wherein the polymeris made in the absence of adding a cobalt compound to the polymerizationreactants.
 43. The process of claim 40, wherein the polymer is made inthe absence of a titanium catalyst.
 44. The process of claim 40, whereinthe polyester polymer is obtained by reacting: (I) a carboxylic acidcomponent comprising at least 80 mole % of the residues of terephthalicacid or derivates of terephthalic acid, and (ii) a hydroxyl componentcomprising at least 80 mole % of the residues of ethylene glycol orpropane diol, based on 100 mole percent of carboxylic acid component and100 mole percent of hydroxyl component in the polyester polymer.
 45. Theprocess of claim 40, wherein the solution is added after 90% conversionin esterification.
 46. The process of claim 40, wherein the solution isadded at inception of or during polycondensing a polyester polymer. 47.The process of claim 40, wherein M comprises Li.
 48. The process ofclaim 40, wherein the molar ratio of M:Al ranges from 0.75:1 to 1.2:1.49. The process of claim 40, wherein the concentration of Al is at least3000 ppm.
 50. The process of claim 40, wherein the concentration of Alis at least 3000 ppm, the molar ratio of M:Al ranges from 0.75:1 to1.3:1, and M comprises Li.
 51. The process of claim 40, wherein thesolution is sufficiently stable such that, if measured, no precipitationis visible to the naked eye when the solution is allowed to stand stillover a period of period of at least one (1) week at ambient conditions.52. The process of claim 40, wherein the solution is sufficiently stablesuch that, if measured, no precipitation is visible to the naked eyewhen the solution is allowed to stand still over a period of period ofat least three (3) weeks at ambient conditions.
 53. The process of anyone of claim 40-52, wherein the solvent comprises 1,3-propane diol,1,4-butane diol, 1,5-pentane diol, or combinations thereof.
 54. Aprocess for making a solution, comprising combining: (i) M, wherein M isrepresented by an alkaline earth metal or alkali metal and (ii) aluminummetal and (iii) a polyhydroxyl solvent having at least 3 carbon atomsand at least two primary hydroxyl groups, the longest carbon chain beinga hydrocarbon; wherein the molar ratio of M:Al ranges from 0.75:1 toless than 1.5:1, heating said solution, and passing a flow of a gas overthe surface of said solution during at least a portion of said heating.55. The process of claim 54, wherein the gas comprises an inert gas. 56.The process of claim 54, wherein the gas comprises at least 90 mole %nitrogen.
 57. The process of claim 56, wherein the flow rate is at least2 SCFH.
 58. The process of claim 57, wherein M comprises Li.
 59. Theprocess of claim 54, comprising heating to a temperature of at least100° C.
 60. The process of any one of claims 54-59, wherein the solventcomprises 1,3-propane diol, 1,4-butane diol, 1,5-pentane diol, orcombinations thereof.